Hydrocracking catalyst for hydrocarbon oil, method for producing hydrocracking catalyst, and method for hydrocracking hydrocarbon oil with hydrocracking catalyst

ABSTRACT

The present invention relates to a hydrocracking catalyst for hydrocarbon oil comprising a support containing a framework-substituted zeolite-1 in which zirconium atoms and/or hafnium atoms form a part of a framework of an ultrastable y-type zeolite and a hydrogenative metal component carried thereon and a method for producing the same. The hydrocracking catalyst of the present invention makes it easy to diffuse heavy hydrocarbon oils such as VGO, DAO and the like into mesopores, is improved in a cracking activity and makes it possible to obtain a middle distillate at a high yield as compared with catalysts prepared by using zeolite comprising titanium and/or zirconium carried thereon.

RELATED APPLICATIONS

This application is a CONTINUATION of U.S. patent application Ser. No13/809,297 filed Mar. 27, 2013, which is a § 371 of PCT/US2011/046272filed Aug. 2, 2011 and claims priority from Japanese Patent No.2010-173665 filed Aug. 2, 2010, all incorporated by reference in theirentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates particularly to a hydrocracking catalystfor hydrocarbon oil, the catalyst being capable of producing middledistillates (kerosene and gas oil; kerosene-gas oil) from heavyhydrocarbons, such as vacuum gas oil (hereinafter, also referred to as“VGO”) and deasphalted oil (also referred to as “DAO”), in high yield.

2. Description of the Related Art

Hitherto, hydrotreating catalysts including zeolites in which titaniumand/or zirconium is carried on (combined with) on mesopores have beenused for treating bottom oil (see, for example, Japanese UnexaminedPatent Application Publication Nos. 2000-334305, 2002-255537, and2003-226519).

For example, Japanese Unexamined Patent Application Publication No.2000-334305 discloses a hydrogenation catalyst including a hydrogenativemetal carried on a catalyst support that is composed of a zeolite inwhich ultrafine particles composed of a titanium-group metal oxide oftitania or zirconia are combined with inner surfaces of mesopores andthat has an atomic ratio of aluminum to silicon in the zeolite, i.e.,[Al]/[Si], of 0.01 to 0.1 (in other words, a molar ratio of SiO₂ toAl₂O₃ (hereinafter referred to as a “SiO₂/Al₂O₃ molar ratio” or “asilica-alumina ratio”) of 20 to 200). It is described therein that thezeolite combined with the ultrafine particles composed of thetitanium-group metal oxide are prepared by bringing a raw-materialzeolite with mesopores into contact with an aqueous solution of atitanium-group metal salt of titania or zirconia at a pH of 0.8 to 2,washing the zeolite with water, drying the resulting zeolite, and firingthe dry zeolite at 400° C. to 600° C.

Japanese Unexamined Patent Application Publication No. 2002-255537discloses a zeolite having a high mesopore content, an atomic ratio ofaluminum to silicon, i.e., [Al]/[Si], of 0.01 to 0.2 (in other words, asilica-alumina ratio of 10 to 200), a volume percent of the mesoporeseach having a pore diameter of 50 to 1000 Å of 30% to 50%, a volume ofthe mesopores of 0.14 cc/g or more, and a proportion of tetracoordinatedaluminum atoms with respect to all aluminum atoms of 25 atomic percentor more, in which metal oxide ultrafine particles of titania and/orzirconia, which is not readily reduced, are combined with inner surfacesof mesopores of the above zeolite, and a hydrotreating catalystincluding a hydrogenative metal carried on a catalyst support composedof the above zeolite. The zeolite having a high mesopore content isprepared by bringing a raw-material zeolite into contact with a stronglyacidic aqueous solution at a pH of 0.8 to 2, drying the zeolite at 50°C. to 200° C., and firing the dry zeolite at 350° C. to 600° C. It isdescribed therein that it is thus possible to prepare a zeolite in whichmetal oxide ultrafine particles are combined with (carried on) innersurfaces of pores.

Japanese Unexamined Patent Application Publication No. 2003-226519discloses a hydrotreating catalyst for hydrocarbon oil, thehydrotreating catalyst including a modified zeolite in which a faujasitezeolite having a crystal lattice constant of 24.28 Å or more and 24.46 Åor less contains a metal element (titanium, zirconium, or hafnium) inthe 4th group of the periodic table, the modified zeolite having a metalelement content of 0.1% to 10% by weight on an elemental metal basis, anAl/Si atomic ratio of 0.01 to 0.1 (in other words, a silica-aluminaratio of 20 to 200), and further containing a hydrogenative metal. It isdescribed therein that the modified zeolite is prepared by bringing afaujasite zeolite having a crystal lattice constant of 24.28 Å to 24.46Å into contact with an aqueous solution containing a water-solublecompound of an element in the 4th group of the periodic table underacidic conditions.

In these hydrotreating catalysts, however, the mesopores are cloggedwith the carried metals, and therefore these catalysts were not suitedin a certain case to hydrotreating (or hydrocracking) of heavyhydrocarbon oil such as VGO and DAO.

As disclosed in WO2007/032232, hydrotreating catalyst including as asupport, a Y-type zeolite containing a titanium atom incorporated into azeolite framework (in other words, a Y-type zeolite in which aluminumatoms constituting the framework are substituted with titanium atoms)has been developed. The above zeolite can be prepared by treating aY-type zeolite with an acidic aqueous solution containing titanium at apH of 1.5 or less, followed by filtering, washing, and drying. Thereby,the zeolite can be made to contain titanium atoms incorporated into azeolite framework structure without clogging mesopores. It is describedthat when the hydrotreating catalyst including the above zeolite as asupport is applied to hydrotreating of heavy hydrocarbon oil, yields ofmiddle distillates are improved because heavy hydrocarbon oil is readilydiffused into mesopores.

SUMMARY OF THE INVENTION

The hydrotreating catalyst including as a support, the zeolite in whicha part of aluminum atoms constituting the zeolite framework is replacedwith titanium atoms, however, has excessively high reactivity(decomposition activity) and excessively decomposes kerosene-gas oil,thus disadvantageously reducing yields of middle distillates.

The present invention has been made in light of the foregoingcircumstances. It is an object of the present invention to provide ahydrocracking catalyst for hydrocarbon oil, the hydrocracking catalystcapable of providing middle distillates in high yield, a method forproducing the hydrocracking catalyst, and a hydrocracking method usingthe hydrocracking catalyst.

The hydrocracking catalyst for hydrocarbon oil according to the presentinvention in accordance with the object described above is ahydrocracking catalyst for hydrocarbon oil comprising a hydrogenativemetal component carried on a support containing an ultra-stable Y-typezeolite, wherein the above ultra-stable Y-type zeolite is aframework-substituted zeolite (hereinafter referred to as aframework-substituted zeolite-1) in which a part of aluminum atomsconstituting a zeolite framework thereof is substituted with zirconiumatoms and/or hafnium atoms.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, 0.1 to 5% by mass of zirconium atoms and/or hafniumatoms in terms of oxides is preferably contained in theframework-substituted zeolite-1 described above.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, the framework-substituted zeolite-1 further containspreferably titanium atoms.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, a part of aluminum atoms constituting the zeoliteframework in the framework-substituted zeolite-1 is replaced preferablywith titanium atoms.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, 0.1 to 5% by mass of titanium atoms in terms of oxideis preferably contained in the framework-substituted zeolite-1.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, the support described above preferably contains theframework-substituted zeolite-1 and inorganic oxides excluding the aboveframework-substituted zeolite-1.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, the inorganic oxide described above is preferablyalumina or silica-alumina.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, the support described above further containspreferably a framework-substituted zeolite (hereinafter referred to as aframework-substituted zeolite-2) in which a part of aluminum atomsconstituting a zeolite framework of the ultra-stable Y-type zeolite issubstituted only with titanium atoms.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, when the support described above contains theframework-substituted zeolite-2, the above framework-substitutedzeolite-2 preferably contains 0.1 to 5% by mass of titanium atoms interms of oxide.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, the support described above preferably comprises theframework-substituted zeolite-1, the framework-substituted zeolite-2 andinorganic oxides excluding the above framework-substituted zeolite-1 andthe above framework-substituted zeolite-2.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, the framework-substituted zeolite-1 contained in thesupport preferably has the following properties (a) to (c):

-   (a) a crystal lattice constant of 2.430 to 2.450 nm,-   (b) a specific surface area of 600 to 900 m²/g and-   (c) a molar ratio of 20 to 100 in terms of SiO₂ to Al₂O₃.

In the hydrocracking catalyst for hydrocarbon oil according to thepresent invention, a specific surface area thereof falls preferably in arange of 200 to 450 m²/g; a volume of pores having a diameter of 600 Åor less falls preferably in a range of 0.40 to 0.75 ml/g; and a carryingamount of the hydrogenative metal component falls preferably in a rangeof 0.01 to 40% by mass.

The method for producing a hydrocracking catalyst for hydrocarbon oil inthe present invention is a method for producing a hydrocracking catalystfor hydrocarbon oil comprising a hydrogenative metal component carriedon a support containing the framework-substituted zeolite-1 in which apart of aluminum atoms constituting a framework of an ultra-stableY-type zeolite is substituted with zirconium atoms and/or hafnium atoms,and the framework-substituted zeolite-1 described above is obtained byfiring an ultra-stable Y-type zeolite having a crystal lattice constantfalling in a range of 2.430 nm or more and 2.450 nm or less, a specificsurface area of 600 to 900 m²/g and a molar ratio of 20 to 100 in termsof SiO₂ to Al₂O₃ at 500 to 700° C., preparing a suspension having a massratio of 5 to 15 in terms of liquid/solid from the above firedultra-stable Y-type zeolite, adding an inorganic acid or an organic acidthereto so that a pH of the above suspension is 1.0 to 2.0, subsequentlyadding a zirconium compound and/or a hafnium compound and mixing themand then neutralizing the suspension.

In another method for producing a hydrocracking catalyst for hydrocarbonoil in the present invention, a zeolite obtained by firing anultra-stable Y-type zeolite having a crystal lattice constant falling ina range of 2.430 nm or more and 2.450 nm or less, a specific surfacearea of 600 to 900 m²/g and a molar ratio of 20 to 100 in terms of SiO₂to Al₂O₃ at 500 to 700° C., preparing a suspension having a mass ratioof 5 to 15 in terms of liquid/solid from the above fired ultra-stableY-type zeolite, adding an inorganic acid or an organic acid thereto sothat a pH of the above suspension is 1.0 to 2.0, subsequently adding azirconium compound and/or a hafnium compound and a titanium compound andmixing them and then neutralizing the mixed solution is used as theframework-substituted zeolite-1.

According to a third aspect of the present invention in accordance withthe object described above, a method for hydrocracking hydrocarbon oilincludes hydrocracking hydrocarbon oil with the hydrocracking catalystdescribed above.

Preferably, the method for hydrocracking hydrocarbon oil according tothe third aspect of the present invention further includes filling areactor vessel of a hydrocracking apparatus which is a flow reactor withthe hydrocracking catalyst, and treating a hydrocarbon oil having aboiling point of 375° C. to 816° C. (707 to 1500° F.) in the presence ofhydrogen at a reactor temperature of 300° C. to 500° C., a hydrogenpressure of 4 to 30 MPa, a liquid hourly space velocity (LHSV) of 0.1 to10 h⁻¹, and a hydrogen/oil ratio of 500 to 2500 Nm³/m³.

Preferably, the method for hydrocracking hydrocarbon oil according tothe third aspect of the present invention further includes filling areactor vessel of a hydrocracking apparatus which is a flow reactor withthe hydrocracking catalyst, and treating a hydrocarbon oil having aboiling point of 375° C. to 650° C. (707 to 1200° F.) in the presence ofhydrogen at a reactor temperature of 330° C. to 450° C., a hydrogenpressure of 7 to 15 MPa, a liquid hourly space velocity (LHSV) of 0.2 to1.5 h⁻¹, and a hydrogen/oil ratio of 1000 to 2000 Nm³/m³ to affordkerosene-gas oil.

In the method for hydrocracking hydrocarbon oil according to the presentinvention, the flow reactor described above is preferably a flow reactorselected from a stirring bath type reactor, a boiling bed type reactor,a baffle-equipped slurry bath type reactor, a fixed bed type reactor, arotary tube type reactor and a slurry bed type reactor.

In the method for hydrocracking hydrocarbon oil according to the presentinvention, the hydrocarbon oil described above contains preferablyrefined oil obtained from (1) crude oil, (2) synthetic crude oil, (3)bitumen, (4) oil sand, (5) shell oil or (6) coal liquid.

In the method for hydrocracking hydrocarbon oil according to the presentinvention, the hydrocarbon oil described above contains refined oilobtained from crude oil, synthetic crude oil, bitumen, oil sand, shelloil or coal liquid, and the above refined oil is preferably any of a)vacuum gas oil (VGO), b) deasphalted oil (DAO) obtained from a solventdeasphalting process or demetalled oil, c) light coker gas oil or heavycoker gas oil obtained from a coker process, d) cycle oil obtained froma fluid catalytic cracking (FCC) process or e) gas oil obtained from avisbraking process.

The hydrocracking catalyst for hydrocarbon oil according to the presentinvention is characterized by that in a hydrocracking catalyst forhydrocarbon oil comprising a hydrogenative metal component carried on asupport containing an ultra-stable Y-type zeolite, the aboveultra-stable Y-type zeolite is the framework-substituted zeolite-1 inwhich a part of aluminum atoms constituting a framework thereof issubstituted with zirconium atoms and/or hafnium atoms.

Accordingly, the hydrocracking catalyst of the present invention makesit easy to diffuse heavy hydrocarbons such as VGO, DAO and the like intomesopores thereof as compared with conventional hydrocracking catalystscomprising a support of a zeolite on which titanium fine particles orzirconium fine particles are carried, and a cracking activity ofhydrocarbon oil is enhanced to make it possible to obtain middledistillates at high yields.

Further, the hydrocracking catalyst of the present invention has aslightly low cracking activity of hydrocarbon oils as compared withthose of conventional hydrocracking catalysts comprising a hydrogenativemetal component carried on a support comprising a framework-substitutedzeolite in which a part of aluminum atoms constituting a framework of aY-type zeolite is substituted with titanium atoms, but an excessivecracking reaction of kerosene & gas oil is inhibited, so that middledistillates can be obtained at high yields. Also, the hydrocrackingcatalyst for hydrocarbon oil according to the present invention isincreased the number of active sites and therefore is provided with ahigh hydrocracking activity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is UV-vis-NIR spectra of USY (A), USY (c) and ZrO₂.

FIG. 2 is UV-vis-NIR spectra of USY (A), USY (D) and ZrO₂.

FIG. 3 is UV-vis-NIR spectra of USY (A) and USY (H). In all of USY (A),USY (H) and USY (D), peaks are observed in the vicinity of a wavelengthof 208 nm as is the case with ZrO₂. USY (c) is a spectrum of anultra-stable Y-type zeolite which is a raw material for USY (A), USY (G)and USY (E).

FIG. 4 is FT-IR spectra of USY (A), USY (G), USY (E) and USY (c). USY(A): a peak based on Si—O—Zr is observed in the vicinity of a wavelengthof 960 cm⁻¹. This shows that USY (A) is a framework-substituted zeolitein which a part of Al atoms constituting a zeolite framework of USY (A)is substituted with Zr atoms. USY (G): a peak based on Si—O—Ti isobserved in the vicinity of a wavelength of 960 cm⁻¹. This shows thatUSY (G) is a framework-substituted zeolite in which a part of Al atomsconstituting a zeolite framework of USY (A) is substituted with Tiatoms. USY (E): peaks based on Si—O—Zr and Si—O—Ti are observed in thevicinity of a wavelength of 960 cm⁻¹. This shows that USY (E) is aframework-substituted zeolite in which a part of Al atoms constituting azeolite framework of USY (A) is replaced with Zr atoms and/or Ti atoms.USY (c): USY (c) is an ultra-stable Y-type zeolite which is a rawmaterial for USY (A), USY (G) and USY (E).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hydrocracking Catalyst for Hydrocarbon Oil

The hydrocracking catalyst for hydrocarbon oil according to the presentinvention comprises a hydrogenation-active metal component carried on asupport containing a framework-substituted zeolite-1 that containszirconium atoms and/or hafnium atoms partially constituting a frameworkof an ultra stable Y-type zeolite (hereinafter, also referred to as“USY”). In the present specification, “the hydrocracking catalyst forhydrocarbon oil according to the present invention” shall be referred toas “the hydrocracking catalyst according to the present invention”, and“the method for producing a hydrocracking catalyst for hydrocarbon oilaccording to the present invention” shall be referred to as “the methodfor producing a hydrocracking catalyst according to the presentinvention”.

The hydrocracking catalyst according to the present invention shall beexplained below in details.

(1) Framework-substituted Zeolite-1 (Constitution)

The framework-substituted zeolite-1 in the present invention is anultra-stable Y-type zeolite in which silicon atoms and aluminum atomsform a zeolite framework and in which a part of the aluminum atoms issubstituted with zirconium atoms and/or hafnium atoms (hereinafter, theframework-substituted zeolite-1 in which a part of aluminum atomsforming a zeolite framework is substituted only with zirconium atoms isreferred to as a “zirconium-substituted zeolite” or “Zr-USY”; theframework-substituted zeolite-1 in which a part of aluminum atomsforming a zeolite framework of the framework-substituted zeolite-1 issubstituted only with hafnium atoms is referred to as a“hafnium-substituted zeolite” or “Hf-USY”; and similarly, theframework-substituted zeolite-1 in which a part of aluminum atomsforming a zeolite framework is substituted only with zirconium atoms andhafnium atoms is referred to as a “zirconium⋅hafnium-substitutedzeolite” or “Zr.Hf-USY”). Zirconium atoms and/or hafnium atoms which aresubstituted for the aluminum atoms forming a framework of theultra-stable Y-type zeolite serve as constituents of the framework ofthe ultra stable Y-type zeolite. In this respect, “substitution” in thepresent invention differs from “carrying” in which zirconium atomsand/or hafnium atoms or particles thereof are attached to the outside ofthe framework of the ultra stable Y-type zeolite, and it differs as wellfrom “combination” prescribed in claim 3 of the patent document 2(Japanese Unexamined Patent Application Publication No. 2002-255537)described above. In the framework-substituted zeolite-1 according to thepresent invention, zirconium atoms and/or hafnium atoms may optionallybe “carried” thereon or “combined” therewith, as prescribed in claim 3of the patent document 2, in the form of, for example, an oxide.

The fact that substitution occurs can be verified by, for example,ultraviolet, visible, and near-infrared spectrophotometry (UV-Vis-NIR),Fourier transform infrared spectroscopy (FT-IR), or nuclear magneticresonance spectrometry (NMR). Note that in the framework-substitutedzeolite in which the framework of a β-zeolite is substituted byzirconium atoms, it is known that a UV spectrum indicating the presenceof zirconium atoms is shown in the range of about 200 to about 220 nm(for example, see FIG. 3 in “B. Rakshe et al., Journal of Catalysis 188,252, 1999”).

In the framework-substituted zeolite-1 in the present invention, a partof aluminum atoms forming a zeolite framework thereof has to besubstituted with (I) zirconium atoms, (II) hafnium atoms or (III)zirconia and hafnium atoms.

The framework-substituted zeolite-1 in the present invention preferablycontains 0.1% to 5% and more preferably 0.2% to 4% zirconium atomsand/or hafnium atoms by mass in terms of oxide (i.e., “ZrO₂” and “HfO₂”)based on the framework-substituted zeolite-1. Further, a range of 0.3 to3% by mass is more preferably recommended.

In this regard, a content range (based on oxides) of zirconium atomsand/or hafnium atoms includes all of the contents of zirconium atomsand/or hafnium atoms substituted for aluminum atoms forming a zeoliteframework and zirconium atoms and/or hafnium atoms which are notsubstituted for the above aluminum atoms.

A zirconium atom and/or hafnium atom content of theframework-substituted zeolite-1 of less than 0.1% by mass in terms ofoxide based on a mass of the framework-substituted zeolite-1 does notresult in an effective amount of a solid acid for a hydrocrackingreactor when a hydrocracking catalyst prepared by using the aboveframework-substituted zeolite-1 as a support is applied to ahydrocracking reactor, and it is thus liable to cause a reduction inactivity of a hydrocracking reactor of hydrocarbon oil.

Similarly, a zirconium atom and/or hafnium atom content exceeding 5% bymass in terms of oxide based on a mass of the framework-substitutedzeolite-1 does not result in an effective pore volume for ahydrocracking reactor of hydrocarbon oil, and it is thus liable to causea reduction in activity of a hydrocracking reactor of hydrocarbon oil.

When the framework-substituted zeolite-1 in the present inventioncontains the zirconium atoms and the hafnium atoms described above, amass ratio (in terms of oxides) of the zirconium atoms to the hafniumatoms shall not specifically be restricted.

The zirconium atom and/or hafnium atom content of theframework-substituted zeolite-1 can be measured with, for example, anX-ray fluorescence analyzer, a high frequency plasma emissionspectrometer, an atomic absorption spectrometer or the like.

In the framework-substituted zeolite-1 described above, zirconium atomsand/or hafnium atoms may optionally be “carried” thereon or “combined”therewith as prescribed in claim 3 of the patent document 2 in the formof, for example, oxide. In this case, zirconium atoms may be, asdescribed above, carried or combined in the form of zirconium oxideparticles. Also, hafnium atoms may be, as described above, carried orcombined in the form of hafnium oxide particles.

When the above particles are present, a particle diameter thereof ispreferably 50 nm or less. A particle diameter of the zirconium particlesand/or hafnium particles each described above exceeding 50 nm, in somecases, does not result in an effective pore volume for a hydrotreatingreactor and is liable to cause clogging of pores. Thus, activity inhydrogenation and dehydrogenation with the hydrocracking catalystincluding the zeolite described above tends to decrease. The particlediameters of the zirconium particles and the hafnium particles eachdescribed above can be measured from a photograph taken with a scanningelectron microscope (SEM).

The framework-substituted zeolite-1 in the present invention may containtitanium atoms in addition to zirconium atoms and/or hafnium atoms, andthe above titanium atoms are more preferably contained in such a mannerthat titanium atoms are partially substituted for a part of aluminumatoms forming the zeolite framework.

To be specific, titanium atoms are contained in theframework-substituted zeolite-1 described above in a proportion ofpreferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass in termsof oxide (that is, TiO₂) on a mass basis of the framework-substitutedzeolite-1. Also, a proportion of 0.6 to 3% by mass is further preferablyrecommended.

In this regard, if a content of the above titanium atoms in theframework-substituted zeolite-1 is less than 0.1% by mass in terms ofoxide, an amount of a solid acid which is effective for a hydrocrackingreactor is not obtained when a hydrocracking catalyst prepared by usingthe above framework-substituted zeolite-1 as a support is applied to ahydrocracking reactor, and therefore an activity of hydrocarbon oil in ahydrocracking reactor tends to be reduced. Similarly, if a content oftitanium atoms in the framework-substituted zeolite-1 exceeds 5% by massin terms of oxide, a pore volume which is effective for a hydrocrackingreactor is not obtained when a hydrocracking catalyst prepared by usingthe above framework-substituted zeolite-1 as a support is applied to ahydrocracking reactor, and therefore an activity of hydrocarbon oil in ahydrogenation reactor and a hydrocracking reactor tends to be reduced. Acontent of titanium atoms in the framework-substituted zeolite-1 can bemeasured by, for example, an X-ray fluorescence analyzer, a highfrequency plasma emission spectrometer, an atomic absorptionspectrometer or the like.

(2) Framework-substituted Zeolite-2 (Constitution)

In the hydrocracking catalyst according to the present invention, aframework-substituted zeolite (hereinafter referred to as “aframework-substituted zeolite-2”) in which a part of aluminum atomsforming the ultra-stable Y-type zeolite is substituted only withtitanium atoms and/or an inorganic acid (limited to inorganic acidswhich do not correspond to those used in the framework-substitutedzeolite-1) in addition to the framework-substituted zeolite-1 describedabove may be contained as a support. Titanium atoms which are notsubstituted for the above aluminum atoms may be contained in theframework-substituted zeolite-2 (“the framework-substituted zeolite-2”is referred to as “the titanium-substituted zeolite” or “Ti-USY”).

The framework-substituted zeolite-2 can be prepared by, for example, amethod described in WO2007/032232 (patent document 4).

The above framework-substituted zeolite-2 preferably contains 0.1% to 5%and more preferably 0.5% to 4% titanium atoms by mass on an oxide (i.e.,“TiO₂”) basis with respect to the framework-substituted zeolite-2. Acontent of 0.6 to 3% by mass is further preferably recommended.

A content range (based on oxide) of the above titanium atoms includesall of the contents of titanium atoms substituted for aluminum atomsforming a zeolite framework and titanium atoms which are not substitutedfor the above aluminum atoms.

In this regard, A titanium atom content of each of theframework-substituted zeolite-2 of less than 0.1% by mass on an oxidebasis does not result in an effective amount of a solid acid for ahydrocracking reactor and is thus liable to cause a reduction in anactivity of hydrocarbon oil in a hydrocracking reactor. The contentexceeding 5% by mass does not result in an effective pore volume for ahydrocracking reactor and is thus liable to cause a reduction in anactivity of hydrocarbon oil in a hydrogenation reactor and ahydrocracking reactor.

The titanium content of the framework-substituted zeolite-2 is measuredwith, for example, an X-ray fluorescence analyzer, a high frequencyplasma emission spectrometer, an atomic absorption spectrophotometer orthe like. In this regard, a crystal lattice constant, a specific surfacearea, a silica-alumina ratio, a crystallinity and a volume of poreshaving a pore diameter of 600 Å or less in the framework-substitutedzeolite-2 are selected preferably from the same ranges as in theframework-substituted zeolite-1.

(3) Characteristics of Framework-substituted Zeolite-1:

A crystal lattice constant, a specific surface area, a molar ratio ofSiO₂ to Al₂O₃, that is, a silica-alumina ratio and the like in theframework-substituted zeolite-1 in the present invention fall preferablyin predetermined ranges.

(a) Lattice Constant (UD)

The framework-substituted zeolites-1 in the present invention each havea crystal lattice constant of preferably 2.430 to 2.450 nm and morepreferably 2.435 to 2.445 nm. A crystal lattice constant of aframework-substituted zeolite of less than 2.430 nm is liable to cause areduction in the activity of the hydrocracking catalyst prepared byusing the framework-substituted zeolite-1 as a support because of a highSiO₂/Al₂O₃ molar ratio in the framework structure of the zeolite and asmall number of solid acid sites serving as active sites for thedecomposition of hydrocarbons.

A crystal lattice constant of the framework-substituted zeolite-1exceeding 2.450 nm results in breakage of the crystal structure of theframework-substituted zeolite-1 during a hydrocracking reactor becauseof a low heat resistance of the framework-substituted zeolite-1 and isthus liable to cause a reduction in the activity of the hydrocrackingcatalyst prepared by using the framework-substituted zeolite-1 as asupport.

A crystal lattice constant of the framework-substituted zeolite-2described above also is preferably 2.430 to 2.450 nm, more preferably2.435 to 2.445 nm. A reason why the above crystal lattice constant rangeis preferred is the same as in a case of the framework-substitutedzeolite-1.

Here, the crystal lattice constant can be measured by reference to anASTM method: The angle of Kα at the (111) plane of titanium oxide(anatase) is determined using silicon (Si) serving as a primaryreference material. X-ray diffraction peaks from the (533) and (642)planes of Y zeolite are measured using titanium oxide serving as asecondary reference material.

(b) Specific Surface Area (SA):

The framework-substituted zeolite-1 in the present invention preferablyhas a specific surface area of 600 to 900 m²/g and more preferably 650to 800 m²/g. This specific surface area is a value determined by the BETmethod using nitrogen adsorption.

A specific surface area of the framework-substituted zeolite-1 of lessthan 600 m²/g, in some cases, results in a reduction in the number ofsolid acid sites effective for a hydrotreating reactor, so that acatalyst activity of the hydrocracking catalyst prepared by using theabove framework-substituted zeolite as a support is unsatisfactory. Aframework-substituted zeolite having a specific surface area exceeding900 m²/g is difficult to produce.

The framework-substituted zeolite-2 also has preferably a specificsurface area of 600 to 900 m²/g, more preferably 650 to 800 m²/g. Areason why the above specific surface area range is preferred is thesame as in a case of the framework-substituted zeolite-1.

(c) Molar Ratio of SiO₂ to Al₂O₃ (Silica-alumina Ratio):

The framework-substituted zeolite-1 in the present invention preferablyhas a molar ratio of SiO₂ to Al₂O₃ (silica-alumina ratio) of 20 to 100and more preferably 25 to 80.

A silica-alumina ratio of the framework-substituted zeolite-1 of lessthan 20 does not result in an effective pore volume for a hydrotreatingreactor and is thus liable to cause a reduction in activity inhydrogenation and hydrocracking reaction with the hydrocracking catalystprepared by using the framework-substituted zeolite as a support.

A silica-alumina ratio of the framework-substituted zeolite-1 exceeding100 is liable to cause a reduction in activity in a decompositionreactor with the hydrocracking catalyst prepared by using theframework-substituted zeolite because of a small number of solid acidsites effective for a hydrotreating reactor.

The framework-substituted zeolite-2 also has preferably a silica-aluminaratio of 20 to 100, more preferably 25 to 80. A reason why the aboverange of the silica-alumina ratio is preferred is the same as in a caseof the framework-substituted zeolite-1.

(d) Crystallinity:

The framework-substituted zeolites-1 have a crystallinity of preferably80% or more. A crystallinity of less than 80% does not provide a desiredeffect of a hydrocracking catalyst including the framework-substitutedzeolite as a support. The framework-substituted zeolite-1 desirably hasa crystallinity of 100% to 130%.

A crystallinity of the framework-substituted zeolite-2 tends to be thesame as in a case of the framework-substituted zeolite-1.

In this regard, the crystallinity is determined as follows: The totalheight (H) of peaks from the (331), (511), (440), (533), (642), and(555) planes of a framework-substituted zeolite measured by X-raydiffraction is determined. The total height (H₀) of peaks from the sameplanes of a commercially available Y zeolite (SK-40, manufactured byUnion Carbide Corporation) is determined as a reference. Thecrystallinity is determined using the following formula (1):Crystallinity (%)=H/H₀×100  (1)

The framework-substituted zeolite-2 also has a crystallinity ofpreferably 80% or more. A reason why the above crystallinity range ispreferred is the same as in a case of the framework-substitutedzeolite-1.

(4) Method for Producing the Framework-substituted Zeolite-1

The framework-substituted zeolite-1 in the present invention can beproduced by, for example, a method described below.

The framework-substituted zeolite-1 is produced by firing an ultrastable Y-type zeolite at 500° C. to 700° C., the ultra stable Y-typezeolite having a crystal lattice constant of 2.430 to 2.450 nm, aspecific surface area of 600 to 900 m²/g, and a molar ratio of SiO₂ toAl₂O₃ of 20 to 100, forming a suspension containing the fired ultrastable Y-type zeolite, the suspension having a liquid/solid mass ratioof 5 to 15, adding an inorganic acid or an organic acid so that a pH ofthe above suspension is 1.0 to 2.0, subsequently adding a solutioncontaining a zirconium compound and/or a hafnium compound and mixingthem and neutralizing the solution with, for example, an aqueous ammoniain such a manner that the mixed solution has a pH of about 7. The aboveproduction method shall be described below in details.

a) Ultra-stable Y-type Zeolite:

Ultra stable Y-type zeolite is used as one of the raw materials for theframework-substituted zeolite-1 in the present invention. Theultra-stable Y-type zeolite is publicly known, and a production methodtherefor shall not specifically be restricted. The ultra-stable Y-typezeolite in the present invention means zeolite having a crystal latticeconstant (UD) falling in a range of 2.430 nm or more and 2.450 nm orless, a specific surface area of 600 to 900 m²/g and a molar ratio(silica-alumina ratio) falling in a range of 20 to 100 in terms of SiO₂to Al₂O₃.

In a production method for the above ultra-stable Y-type zeolite, aY-type zeolite (Na—Y) synthesized by a common method is subjected toexchange of sodium ions with ammonium ions by a conventional method (forexample, dispersing Y-type zeolite in water to prepare a suspension,adding ammonium sulfate thereto, then washing the solid matter withwater, next washing it with an ammonium sulfate aqueous solution of atemperature of 40 to 80° C., subsequently washing it with water of 40 to95° C. and then drying it at 100 to 180° C. for 30 minutes) to obtain anammonium-exchanged Y-type zeolite (NH₄—^(50 to 70)Y) in which 50 to 70%of Na contained in the Y-type zeolite is substituted with NH₄.

Subsequently, a hydrogen type Y-type zeolite (HY) is prepared bycalcining the above ammonium-exchanged Y-type zeolite (NH₄—^(50 to 70)Y)at 500 to 800° C. for 10 minutes to 10 hours in a saturated vaporatmosphere. Then, an ammonium-exchanged Y-type zeolite(NH₄—^(80 to 97)Y) in which 80 to 97% of Na contained in the initialY-type zeolite (Na—Y) is ion-exchanged with NH₄ can be obtained bydispersing the hydrogen type Y-type zeolite obtained above in water of40 to 95° C. to prepare a suspension, further adding ammonium sulfatethereto, then stirring the suspension at 40 to 95° C. for 10 minutes to3 hours, further washing the solid matter with water of 40 to 95° C.,next washing it with an ammonium sulfate aqueous solution of 40 to 95°C., subsequently washing it with water of 40 to 80° C. and then dryingit at 100 to 180° C. for 30 minutes to 30 hours. In this respect, thefinal ammonium ion exchange rate is preferably 90% or more.

The ammonium-exchanged Y zeolite (NH₄—^(80 to 97)Y) thus obtained iscalcined at 500 to 700° C. for 10 minutes to 10 hours in, for example, asaturated vapor atmosphere, whereby capable of being prepared is aultra-stable Y-type zeolite (USY) having a crystal lattice constant (UD)of 2.430 nm or more and 2.450 nm or less, a specific surface area of 600to 900 m²/g and a molar ratio (silica-alumina ratio) of SiO₂ to Al₂O₃ of20 to 100.

It is important for obtaining the desired framework-substitutedzeolite-1 to control a crystal lattice constant of the ultra-stableY-type zeolite to 2.430 to 2.450 nm.

In the method for producing the hydrocracking catalyst according to thepresent invention, extraskeletal aluminum (aluminum atoms which do notform the zeolite framework) may be removed from the ultra-stable Y-typezeolite described above which is the raw material in order to obtain theultra-stable Y-type zeolite having a crystal lattice constant of 2.430to 2.450 nm. Extraskeletal aluminum can be removed by, for example, amethod of dispersing the ultra-stable Y-type zeolite described above inwarm water of 40 to 95° C. to prepare a suspension, adding sulfuric acidto the above suspension and stirring it for 10 minutes to 3 hours whilemaintaining the temperature at 40 to 95° C. to thereby dissolve theextraskeletal aluminum. An addition amount of sulfuric acid shall notspecifically be restricted as long as it is an amount by whichextraskeletal aluminum can be dissolved to a desired level. Afterdissolving the extraskeletal aluminum, the suspension is filtrated, anda residue on the filter is washed with purified water of 40 to 95° C.and dried at 100 to 180° C. for 3 to 30 hours, whereby an ultra-stableY-type zeolite from which the extraskeletal aluminum is removed can beobtained.

In the method for producing the hydrocracking catalyst according to thepresent invention, the ultra-stable Y-type zeolite which is the rawmaterial is calcined at 500° C. to 700° C., preferably 550° C. to 650°C. The calcining time shall not specifically be restricted as long asthe targeted framework-substituted zeolite-1 is obtained, and it iscalcined in a range of, for example, 30 minutes to 10 hours. If acalcining temperature of the ultra-stable Y-type zeolite is lower than500° C., a framework substitution amount of zirconium atoms, hafniumatoms and titanium atoms tends to be reduced when carrying out frameworksubstitution treatment by zirconium atoms, hafnium atoms or titaniumatoms at a subsequent step as compared with a case in which calcining iscarried out at 500° C. to 700° C. If the calcining temperature exceeds700° C., a specific surface area of the ultra-stable Y-type zeolite islowered, and a framework substitution amount of zirconium atoms, hafniumatoms and titanium atoms is reduced when carrying out frameworksubstitution treatment by zirconium atoms, hafnium atoms or titaniumatoms at a subsequent step, so that zirconium atoms, hafnium atoms andtitanium atoms come to be present in a particular form. In respect to acalcining atmosphere of the ultra stable Y-type zeolite, it is carriedout preferably in the air.

The calcined ultra-stable Y-type zeolite is suspended in water having atemperature of about 20° C. to about 30° C. to form a suspension. Withrespect to the concentration of the suspension of the ultra-stableY-type zeolite, the liquid/solid mass ratio is preferably in the rangeof 5 to 15, and more preferably, a mass ratio of 8 to 12 is recommended.

Next, an inorganic acid or an organic acid is added thereto so that a pHof the suspension described above is controlled to 1.0 to 2.0, andsubsequently a solution containing a zirconium compound and/or a hafniumcompound is added and mixed. Then, the mixed solution is neutralized (pH7.0 to 7.5) and dried desirably at 80 to 180° C., whereby theframework-substituted zeolite-1 described above can be obtained.

Sulfuric acid, nitric acid, hydrochloric acid and the like can be givenas the above inorganic acid used, and among them, sulfuric acid,hydrochloric acid and the like are particularly preferred. Further,carboxylic acids can suitably be used as the organic acid describedabove. A use amount of the inorganic acid or the organic acid shall notbe restricted as long as a pH of the suspension can be controlled to arange of 1.0 to 2.0, and it is, for example, a 0.5- to 4.0-fold molaramount and preferably 0.7- to 3.5-fold molar amount based on an amountof Al₂O₃ in the ultra-stable Y-type zeolite, but it shall not berestricted to the above range.

Examples of the zirconium compound described above include zirconiumsulfate, zirconium nitrate, zirconium chloride and the like. Among thesecompounds, zirconium sulfate, zirconium nitrate, and the like areparticularly preferred. The amount of the zirconium compound added ispreferably 0.1% to 5% by mass and more preferably 0.2% to 4% by mass ona zirconium oxide basis with respect to the ultra-stable Y-type zeolitedescribed above. The addition of the zirconium compound in an amount ofless than 0.1% by mass fails to improve solid acid of the zeolite. Theaddition of the zirconium compound in an amount exceeding 5% by mass maycause clogging of pores of the zeolite. Usually, an aqueous solution ofa zirconium compound prepared by dissolving the zirconium compound inwater is suitably used as the zirconium compound.

Examples of the hafnium compound described above include hafniumchloride, hafnium nitrate, hafnium fluoride, hafnium bromide, hafniumoxalate and the like. Among these compounds, hafnium chloride, hafniumnitrate, and the like are particularly preferred. The amount of thehafnium compound added is preferably 0.1% to 5% by mass and morepreferably 0.2% to 4% by mass on a hafnium oxide basis with respect tothe ultra-stable Y-type zeolite. The addition of the hafnium compound inan amount of less than 0.1% by mass cannot improve a solid acid of thezeolite. The addition of the hafnium compound in an amount exceeding 4%by mass makes the resulting catalyst expensive. Usually, an aqueoussolution of a hafnium compound prepared by dissolving the hafniumcompound in water is suitably used as the hafnium compound.

Here, a titanium compound may be added to the mixed solution describedabove. Examples of the titanium compound include titanium sulfate,titanium acetate, titanium chloride, titanium nitrate, and titaniumlactate. Among these compounds, titanium sulfate, titanium acetate, andthe like are particularly preferred. The amount of the titanium compoundadded is preferably 0.1% to 5% by mass and more preferably 0.2% to 4% bymass on an oxide basis with respect to the ultra stable Y-type zeolite.The addition of the titanium compound in an amount of less than 0.1% bymass causes lack of solid acid sites of the zeolite. The addition of thetitanium compound in an amount exceeding 5% by mass may cause cloggingof pores of the zeolite. Usually, an aqueous solution of a titaniumcompound prepared by dissolving the titanium compound in water issuitably used as the titanium compound.

A pH of the above suspension has to be controlled in advance to 1.0 to2.0 for the purpose of preventing precipitation from being generated inmixing an aqueous solution of the zirconium compound, the hafniumcompound or the titanium compound with a suspension of the ultra-stableY-type zeolite described above.

In the case of mixing an aqueous solution of the zirconium compound, thehafnium compound or the titanium compound with a suspension of theultra-stable Y-type zeolite, preferably, the above aqueous solution isgradually added to the suspension. After finishing addition of theaqueous solution described above to the suspension, the solution ispreferably mixed by stirring at, for example, room temperature (about25° C. to about 35° C.) for 3 to 5 hours.

Further, after finishing the mixing described above, the mixed solutiondescribed above is neutralized by adding an alkali such as aqueousammonia and the like so that a pH thereof is controlled to 7.0 to 7.5,whereby the framework-substituted zeolite-1 in the present invention canbe obtained.

In this regard, when only the zirconium compound (or an aqueous solutionthereof) is used as the compound (or an aqueous solution thereof) addedto the suspension described above, the framework-substituted zeolite-1(Zr-USY) in which zirconium atoms is substituted for a part of aluminumatoms forming the framework of the ultra-stable Y-type zeolite isformed; when only the hafnium compound (or an aqueous solution thereof)is used, the framework-substituted zeolite-1 (Hf-USY) in which hafniumatoms is substituted for a part of aluminum atoms forming the frameworkof the ultra stable Y-type zeolite is formed; and when the zirconiumcompound and the hafnium compound (or aqueous solutions thereof) areused, the framework-substituted zeolite-1 (Zr.Hf-USY) in which zirconiumatoms and hafnium atoms are substituted for a part of aluminum atomsforming the framework of the ultra-stable Y-type zeolite is formed.

When the titanium compound (or an aqueous solution thereof) is added incombination in adding the zirconium compound and/or the hafnium compound(or aqueous solutions thereof) to the suspension described above, theframework-substituted zeolite-1 (Zr.Hf.Ti-USY) in which zirconium atoms,hafnium atoms and titanium atoms form a part of the framework of theultra-stable Y-type zeolite is formed.

The resulting framework-substituted zeolite-1 is preferably filtered, ifdesired, washed with water, and dried at about 80° C. to about 180° C.

(5) Carrier:

In the hydrocracking catalyst according to the present invention, thesupport described above contains the framework-substituted zeolite-1described above. The support described above can contain an inorganicoxide excluding the above framework-substituted zeolite-1 and/or theframework-substituted zeolite-2 in addition to the framework-substitutedzeolite-1 described above.

The inorganic oxide described above typically contains a substanceserving as a granulating agent or a binder. Usually, a known substancethat is contained in a support including the ultra-stable Y-type zeoliteand that is used as a granulating agent or the like can be used. As theinorganic oxide, a hydrocracking catalyst used in the related art and aporous inorganic oxide for use in hydrotreating catalysts can be used.Examples thereof include alumina, silica, titania, silica-alumina,alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina,silica-alumina-boria, phosphorus-alumina-boria,phosphorus-alumina-silica, silica-alumina-titania, andsilica-alumina-zirconia. In the present invention, in particular, aninorganic oxide mainly composed of alumina, silica-alumina is preferred.

The framework-substituted zeolite-1 content and the inorganic oxidecontent of the support can be appropriately determined according to theobject. The support has a framework-substituted zeolite-1 content of 2%to 80% by mass and preferably 20% to 70% by mass and an inorganic oxidecontent of 98% to 20% by mass and preferably 80% to 30% by mass. Whenthe framework-substituted zeolite-1 and the framework-substitutedzeolite-2 are used in combination, they are used preferably in aproportion of less than 50% in a sum of the framework-substitutedzeolite-1 and the framework-substituted zeolite-2.

(6) Hydrogenative Metal Component:

As the hydrogenative metal component, a known metal component for use inconventional hydrocracking catalysts can be used. Examples thereofinclude metal components (iron, cobalt, nickel, rhodium, palladium,silver, iridium, platinum or gold) in group 8 of the long periodic tableand/or metal components (chromium, molybdenum or tungsten) in group 6.Preferred examples of the metal component include combinations ofmolybdenum or tungsten in group 6 and cobalt or nickel in group 8; andmetal components of the platinum group (platinum, rhodium, palladium andthe like).

The hydrogenative metal component may be contained in the hydrocrackingcatalyst in an amount (0.01 to 40% by mass in terms of oxide) usuallyused in a hydrocracking catalyst used in the related art. In the case ofmolybdenum, tungsten, cobalt or nickel, an amount thereof isparticularly preferably 3 to 30% by mass in terms of oxide based on amass of the catalyst. In the case of the platinum group (platinum,rhodium, palladium and the like), an amount thereof is particularlypreferably 0.01 to 2% by mass in terms of metal.

(7) Properties of Hydrocracking Catalyst for Hydrocarbon Oil:

A specific surface area of the hydrocracking catalyst according to thepresent invention falls preferably in a range of 200 to 450 m²/g.Further, a range of 250 to 400 m²/g is more suitably recommended. If theabove specific surface area is less than 200 m²/g, the decompositionrate is reduced, and a yield of the middle distillate is reduced aswell. If the above specific surface area exceeds 450 m²/g, thedecomposition rate grows high, and the gas fraction tends to beincreased.

In the hydrocracking catalyst according to the present invention, avolume of pores having a pore diameter of 600 Å or less falls preferablyin a range of 0.40 to 0.75 ml/g. Further, the range of 0.45 to 0.70 ml/gis more suitably recommended. If the above pore volume is less than 0.40ml/g, the specific surface area is reduced. Accordingly, thedecomposition rate is reduced, and a yield of the middle distillate isreduced as well. If the above pore volume exceeds 0.75 ml/g, thespecific surface area is elevated. Accordingly, the decomposition rategrows high, and the gas fraction tends to be increased. In thisconnection, the pore volume is determined from pore distributionobtained by calculating and analyzing a desorption data of nitrogen by aBJH method.

In the hydrocracking catalyst according to the present invention, thehydrogenation-active metal component is preferably carried thereon, asdescribed above, in a range of 0.01 to 40% by mass.

An amount of zirconium or hafnium contained in the hydrocrackingcatalyst according to the present invention each is preferably 0.1 to 5%by mass (in terms of oxide) respectively. Further, the range of 0.5 to4% is suitably recommended.

An amount of titanium optionally contained in the hydrocracking catalystaccording to the present invention is preferably 0.1 to 5% by mass (interms of oxide). Further, the range of 0.5 to 4% is suitablyrecommended.

Method for Producing Hydrocracking Catalyst for Hydrocarbon Oil:

The hydrocracking catalyst for hydrocarbon oil according to the presentinvention can be produced as follows: for example, theframework-substituted zeolite-1 is mixed with the inorganic oxidedescribed above (or a precursor thereof). The mixture is formed into anarticle with a desired shape by a common method. The article is driedand fired to form a support. The support is impregnated with thehydrogenative metal component by a common method, dried, and fired,thereby affording the hydrocracking catalyst.

Alternatively, the framework-substituted zeolite-1 and the inorganicoxide (or a precursor thereof) are mixed with the hydrogenative metalcomponent. The mixture is formed into an article with a desired shape.The article is dried and fired, thereby affording the hydrocrackingcatalyst.

The precursor of the inorganic oxide described above shows a substanceto be formed into the inorganic oxide constituting a support of thehydrocracking catalyst by mixing with other catalyst constitutionalcomponents and subjecting to prescribed treatment.

Firing conditions for this type of catalyst used in the related art areapplied to firing of the support and the hydrocracking catalyst. Thefiring temperature is preferably in the range of 400° C. to 650° C.

Usually, the hydrogenating catalyst according to the present inventioncan be prepared by impregnating the support described above with anaqueous solution containing the hydrogenation-active metal component andcalcining it at 400 to 650° C., for example, for 10 minutes to 3 hoursin the air.

Method for Hydrocracking Hydrocarbon Oil:

The hydrocracking catalyst for hydrocarbon oil according to the presentinvention is charged into a reactor vessel of a hydrotreating apparatus(flow reactor) and suitably used for hydrocracking hydrocarbon oil.

The hydrocarbon oil described above contains preferably refined oilobtained from (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4)oil sand, (5) shell oil or (6) coal liquid. Suitably used as the aboverefined oil is oil selected from, for example, a) vacuum gas oil (VGO),b) deasphalted oil (DAO) obtained from a solvent deasphalting process ordemetalled oil, c) light coker gas oil or heavy coker gas oil obtainedfrom a coker process, d) cycle oil obtained from a fluid catalyticcracking (FCC) process or e) gas oil obtained from a visbraking process.

The hydrocracking can be carried out on publicly known conditions.

For example, a hydrotreating apparatus which is a flow reactor reactorapparatus is filled with the hydrocracking catalyst described above, andhydrocarbon oil having a boiling point of 375° C. to 833° C. can betreated in the presence of hydrogen on the conditions of a reactiontemperature of 300° C. to 500° C., a hydrogen pressure of 4 to 30 MPa, aliquid hourly space velocity (LHSV) of 0.1 to 10 h⁻¹ and a hydrogen/oilratio of 500 to 2500 Nm³/m³.

Further, a hydrotreating which is a flow reactor is filled with thehydrocracking catalyst described above, and a hydrocarbon oil having aboiling point of 375° C. to 650° C. can be treated in the presence ofhydrogen on the conditions of a reactor temperature of 330° C. to 450°C., a hydrogen pressure of 7 to 15 MPa, a liquid hourly space velocity(LHSV) of 0.2 to 1.5 h⁻¹ and a hydrogen/oil ratio of 1000 to 2000 Nm³/m³to obtain kerosene & gas oil. Capable of being suitably used as the flowreactor described above is a flow reactor selected from a stirring bathtype reactor, a boiling floor type reactor, a baffle-equipped slurry bedtype reactor, a fixed bed type reactor, a rotary tube type reactor and aslurry bed type reactor.

The hydrocracking catalyst for hydrocarbon oil according to the presentinvention can suitably be used particularly for hydrocracking of highboiling fraction-containing hydrocarbons. The high boilingfraction-containing hydrocarbons mean hydrocarbons in which an amount offractions having a boiling point of 560° C. or higher accounts for 30%by mass or more. The high boiling fraction-containing hydrocarbonsinclude, for example, a vacuum gas oil (VGO), a solvent deasphalted oil(DAO) and the like.

In the case where hydrocarbon oils, for example,high-boiling-fraction-containing hydrocarbons, are hydrocracked usingthe hydrocracking catalyst for hydrocarbon oil according to the presentinvention, middle distillates can be provided in high yield because ofsuppression of the excessive decomposition reactor of kerosene-gas oil,as described above.

Apparatus for Hydrotreating Hydrocarbon Oil:

An apparatus for hydrotreating hydrocarbon oil in the present inventionis not particularly limited as long as the foregoing hydrocracking forhydrocarbon oil can be performed. Various types of apparatuses may beused. An apparatus for hydrotreating hydrocarbon oil including a firstcatalyst-filled tank, a second catalyst-filled tank, and a thirdcatalyst-filled tank that are connected in series is particularlysuitable. Each of the catalyst-filled tanks is filled with ahydrocracking catalyst for hydrocarbon oil.

The second catalyst-filled tank is filled with the hydrocrackingcatalyst according to the present invention. The hydrocracking catalystin the second catalyst-filled tank is used in a filling factor of, forexample, 10% to 60% by volume with respect to the total volume of allthe hydrocracking catalysts filled into the first, second, and thirdcatalyst-filled tanks. However, the filling factor may fall in a rangeother than the above range.

EXAMPLES

Analytical methods used in the present invention shall be describedbelow.

1) Composition Analysis:

An X-ray fluorescence analyzer (“RIX3000” manufactured by RigakuCorporation) was used to carry out composition analysis (Zr, Hf, Ti, Moor Ni) of a sample (zeolite or the hydrocracking catalyst). A sample formeasurement was prepared by a glass bead method. To be specific, 5 g ofthe sample was put in a vinyl chloride-made ring having an innerdiameter of 35 mm and molded by applying a pressure of 20 t for 20seconds by means of a pressure molding machine to prepare the sample formeasurement. Conditions of the X-ray fluorescence analysis are shownbelow; target: Rh, analyzing crystal: LiF, detector: scintillationcounter, excitation: Rh vessel of 4 kW, measuring voltage: 55 kV,current: 70 mA.

2) Measurement of Sodium in Zeolite:

An atomic absorption spectrometer (“Z5300” manufactured by HORIBA Ltd.)was used to measure a sodium content in a sample (zeolite). Themeasuring wavelength range was controlled to 190 to 900 nm.

3) Crystal Lattice Constant:

An X-ray diffractometer (“RINT2100” manufactured by Rigaku Corporation)was used to measure an X-ray diffraction peak of a sample (zeolite), andthe crystal lattice constant was calculated from the result thereof. Amethod for calculating the crystal lattice constant has already beendescribed in the present specification. Conditions of the X-raydiffraction are shown below; vessel: Cu—K (α ray), 2θ scanning range: 20to 50°, scanning speed: 0.01°/minute, scanning step: 0.01°.

4) Crystallinity:

The crystallinity was calculated from an X-ray diffraction peak of asample (zeolite). A calculating method therefor has already beendescribed in the present specification.

5) SiO₂/Al₂O₃ Molar Ratio:

A peak intensity ratio of Si and Al was determined from an X-raydiffraction peak of a sample (zeolite), and it was reduced to a molarratio of SiO₂ to Al₂O₃.

6) Specific Surface Area and Pore Volume:

An adsorption measuring equipment (fully automatic gas adsorptionequipment “AUTOSORB-1” manufactured by Quantachrome InstrumentsCorporate) was used to subject 0.02 to 0.05 g of a sample (zeolite orthe hydrocracking catalyst) to deaeration treatment at room temperaturefor 5 hours, and then an adsorption desorption isothermal curve wasmeasured under liquid nitrogen temperature to calculate a specificsurface area per mass using a BET equation of a multipoint method.Further, a pore distribution and a pore volume (pore diameter: 600 Å orless) were calculated from a nitrogen adsorption isothermal curve by aBJH method.

7) Ultraviolet-visible/Near-infrared/Spectrophotometry (UV-vis-NIRSpectrum):

A UV-vis-NIR spectrum of zeolite was measured by means of anultraviolet-visible/near-infrared/spectrophotometer (model number: JASCOV-570, manufactured by JASCO Corporation). The sample was prepared byphysically mixing potassium bromide with the sample in a proportion of99:1 and molding 50 mg of the mixture into a wafer form at a pressure of500 kg/cm². Then, the molded matter was heated up to 200° C. at aheating rate of 3.0° C./minute and pre-treated by carrying out vacuumevacuation for 3 hours, and then measurement was carried out at roomtemperature on the conditions of a spectral bandwidth of 10 mm and ascanning speed of 400 nm/minute.

8) Fourier Transform Infrared Spectroscopy (FT-IR Spectrum):

FT-IR spectra of a hydroxyl group of zeolite and a framework vibrationarea thereof were measured by means of a transmission Fourier transforminfrared spectroscope (JIR-7000, manufactured by JASCO Corporation). Thesample was prepared by molding 20 mg of the sample into a wafer form ata pressure of 500 kg/cm². Thereafter, the molded matter was heated up to400° C. at a heating rate of 6.7° C./minute and pre-treated by carryingout vacuum evacuation for 3 hours, and then measurement was carried outat room temperature on the conditions of a resolution of 4 cm′ and anintegration frequency of 500 times.

Explanations of Tables:

-   Table 1: the properties of USY (a) to (m) used as the raw materials    were shown in Table 1.-   Table 2: the properties of the framework-substituted zeolite-1    (USY (A) to USY (F)) used in Example 1 to Example 6 were shown in    Table 2.-   Table 3: the properties of the hydrocracking catalysts (Catalyst A    to Catalyst F) prepared in Example 1 to Example 6 were shown in    Table 3.-   Table 4: the properties of the raw material oils used in the test    examples were shown in Table 4.-   Table 5: the test results (relative cracking rates and relative    middle distillate yields) of the hydrocracking catalysts according    to the present invention were shown in Table 5.

Example 1 Hydrocracking catalyst A

Ultra-stable Y Zeolite

First, 50.0 kg of a NaY zeolite (hereinafter, also referred to as “NaY”)having a SiO₂/Al₂O₃ molar ratio of 5.2, a unit cell dimension (UD) of2.466 nm, a specific surface area (SA) of 720 m²/g, and a Na₂O contentof 13.0% by mass was suspended in 500 liter (hereinafter, also expressedas “L”) of water having a temperature of 60° C. Furthermore, 14.0 kg ofammonium sulfate was added thereto. The resulting suspension was stirredat 70° C. for 1 hour and filtered. The resulting solid was washed withwater. Then the solid was washed with an ammonium sulfate solution of14.0 kg of ammonium sulfate dissolved in 500 L of water having atemperature of 60° C., washed with 500 L of water having a temperatureof 60° C., dried at 130° C. for 20 hours, thereby affording about 45 kgof a Y zeolite (NH₄ ⁶⁵Y) in which 65% of sodium (Na) contained in NaYwas ion-exchanged with ammonium ion (NH₄ ⁺). A content of Na₂O in NH₄⁶⁵Y was 4.5% by mass.

NH₄ ⁶⁵Y 40 kg was fired in a saturated water vapor atmosphere at 670° C.for 1 hour to form a hydrogen-Y zeolite (HY). HY was suspended in 400 Lof water having a temperature of 60° C. Then 49.0 kg of ammonium sulfatewas added thereto. The resulting mixture was stirred at 90° C. for 1hour and washed with 200 L of water having a temperature of 60° C. Themixture was then dried at 130° C. for 20 hours, thereby affording about37 kg of a Y zeolite (NH₄ ⁹⁵Y) in which 95% of Na contained in theinitial NaY was ion-exchanged with NH₄. NH₄ ⁹⁵Y 33.0 kg was fired in asaturated water vapor atmosphere at 650° C. for 1 hour, therebyaffording about 15 kg of a ultra stable Y zeolite (hereinafter, alsoreferred to as “USY (a)”) having a SiO₂/Al₂O₃ molar ratio of 5.2 and aNa₂O content of 0.60% by mass. Table 1 shows physical properties of USY(a).

Next, 26.0 kg of this USY (a) was suspended in 260 L of water having atemperature of 60° C. After 61.0 kg of 25% sulfuric acid by mass wasgradually added to the suspension, the suspension was stirred at 70° C.for 1 hour. The suspension was filtered. The resulting solid was washedwith 260 liter of deionized water having a temperature of 60° C. anddried at 130° C. for 20 hours, thereby affording a ultra stable Y-typezeolite (hereinafter, also referred to as “USY (b)”). Table 1 showsphysical properties of USY (b).

USY (b) was fired at 600° C. for 1 hour, thereby affording about 17 kgof ultra stable Y-type zeolite (hereinafter, also referred to as “USY(c)”). Table 1 shows physical properties of USY (c).

Preparation of Zirconium-substituted Zeolite: USY (A)

First, 1 kg of USY (c) was suspended in 10 L of water having atemperature of 25° C. The pH of the suspension was adjusted to 1.6 with25% sulfuric acid by mass. Then 86 g of a solution containing 18%zirconium sulfate by mass was added thereto. The resulting mixture wasstirred for 3 hours at room temperature. Then the pH was adjusted to 7.2with 15% aqueous ammonia by mass. After the mixture was stirred for 1hour at room temperature, the mixture was filtered. The resulting solidwas washed with 10 L of water and dried at 130° C. for 20 hours, therebyaffording about 1 kg of a zirconium-substituted zeolite (hereinafter,also referred to as “USY (A)”). Table 2 shows physical properties of USY(A). FIG. 1 shows a UV spectrum of USY (A).

FIG. 1 demonstrated as follows: The UV spectrum of ZrO₂ derived fromzirconium sulfate serving as a raw material for USY (A) showed peaks atabout 230 and about 280 nm, whereas the UV spectrum of USY (A) showed apeak at about 200 to 220 nm. Thus, the framework of USY (A) wassubstituted by Zr.

Here, the UV spectrum of the zeolite was measured with anultraviolet-visible-near-infrared spectrophotometer (JASCO V-570,manufactured by JASCO Corporation) at a band width of 10 mm and ascanning rate of 400 nm/min. Meanwhile, 50 mg of a potassium bromide-USY(A) 99:1 mixture was formed into a wafer-like UV-spectrum sample at apressure of 500 kg/cm². The sample was placed in theultraviolet-visible-near-infrared spectrophotometer. After pretreatmentwas performed by heating the sample to 200° C. at a heating rate of 3°C./min and evacuating the sample for 3 hours, measurement was performedat room temperature at a resolution of 4 cm⁻¹ and a number ofintegrations of 500.

The composition analysis of the zeolite was performed with an X-rayfluorescence analyzer (RIX 3000, manufactured by Rigaku Corporation). Asample was prepared by a glass bead method. Sodium in the zeolite wasmeasured with an atomic absorption spectrophotometer (Z-5300,manufactured by HORIBA, Ltd). The crystallinity and the crystal latticeconstant were measured with an X-ray diffractometer (RINT 2100,manufactured by Rigaku Corporation). The specific surface area and thepore volume were measured with a pore distribution analyzer (Autosorb,manufactured by Quantachrome Instruments).

Hydrocracking Catalyst A

First, 40 kg of an aqueous solution of 6.8% sodium aluminate by mass onan Al₂O₃ basis was mixed with 40 kg of an aqueous solution of 2.4%aluminum sulfate by mass on an Al₂O₃ basis. Further, the mixture wasstirred at 60° C. for 1 hour, and then the product was washed with 150 Lof a 0.3 mass % ammonia aqueous solution to remove Na₂SO₄. Next, waterwas added to the product from which Na₂SO₄ was removed to adjust anAl₂O₃ concentration to 10% by mass. The pH was adjusted to 10.5 with 15%aqueous ammonia by mass. The mixture was stirred at 95° C. for 10 hours,dehydrated, washed, and kneaded with a kneader, thereby providing analumina mixture.

The resulting alumina mixture was mixed with USY (A) in a dry mass ratioof 1:1. The mixture was kneaded with a kneader, formed into a columnarshape having a diameter of 1.8 mm, and fired at 550° C. for 3 hours,thereby affording support A.

The support A was immersed in an aqueous solution containinghydrogenation-active metal components and fired in the air at 550° C.for 1 hour, thereby affording hydrocracking catalyst A. Here, theaqueous solution containing hydrogenation-active metal components wasprepared by adding 700 mL of water to 201.3 g of molybdenum trioxide (anexample of the hydrogenation-active metal component) and 90.4 g ofnickel carbonate (an example of the hydrogenation-active metalcomponent) and stirring the resulting mixture at 95° C. for 5 hours.Hydrocracking catalyst A contained 0.39% zirconium by mass, 16.7%molybdenum by mass, and 3.88% nickel by mass on an oxide basis. Table 3shows physical properties of hydrocracking catalyst A.

Example 2 Hydrocracking Catalyst B

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by sulfuric acid of 25%by mass. Hafnium chloride 8 g was added and mixed, and the suspensionwas stirred at room temperature for 3 hours. Then, the pH was adjustedto 7.0 to 7.5 by aqueous ammonia of 15% by mass, and the suspension wasstirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a hafnium-substituted type zeolite (hereinafterreferred to as “USY (B)”). The properties thereof are shown in Table 2.

Further, a hydrocracking catalyst B containing USY (B) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst B are shown in Table 3.

Example 3 Hydrocracking Catalyst C

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.5 to 1.7 by sulfuric acidof 25% by mass. Zirconium sulfate of 18% by mass 86 g and hafniumchloride 8 g were added and mixed, and the suspension was stirred atroom temperature for 3 hours. Then, the pH was adjusted to 7.2 byaqueous ammonia of 15% by mass, and the suspension was stirred at roomtemperature for 1 hour and then filtrated. A matter obtained was washedwith 10 L of water and dried at 130° C. for 20 hours to obtain about 1kg of a zirconium⋅hafnium-substituted type zeolite (hereinafter referredto as “USY (C)”). The properties thereof are shown in Table 2.

Further, a hydrocracking catalyst C containing USY (C) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst C are shown in Table 3.

Example 4 Hydrocracking Catalyst D

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by sulfuric acid of 25%by mass. Zirconium sulfate of 18% by mass 86 g, hafnium chloride 8 g andtitanyl sulfate of 33% by mass 60 g were added and mixed, and thesuspension was stirred at room temperature for 3 hours. Then, the pH wasadjusted to 7.2 by aqueous ammonia of 15% by mass, and the suspensionwas stirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a zirconium⋅hafnium⋅titanium-substituted typezeolite (hereinafter referred to as “USY (D)”). The properties of USY(D) are shown in Table 2, and a UV spectrum thereof is shown in FIG. 2.

As shown in FIG. 2, it was confirmed that a UV spectrum of TiO₂ obtainedfrom titanyl sulfate which was the raw material had peaks in thevicinity of 220 and 320 nm and that USY (D) had peaks in the vicinity of210 to 320 nm due to substitution of Zr and Ti.

Further, a hydrocracking catalyst D containing USY (D) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst D are shown in Table 3.

Example 5 Hydrocracking Catalyst E

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by sulfuric acid of 25%by mass. Zirconium sulfate of 18% by mass 86 g and titanyl sulfate of33% by mass 60 g were added and mixed, and the suspension was stirred atroom temperature for 3 hours. Then, the pH was adjusted to 7.2 byaqueous ammonia of 15% by mass, and the suspension was stirred at roomtemperature for 1 hour and then filtrated. A matter obtained was washedwith 10 L of water and dried at 130° C. for 20 hours to obtain about 1kg of a zirconium⋅titanium-substituted type zeolite (hereinafterreferred to as “USY (E)”). The properties of USY (E) are shown in Table2.

Further, a hydrocracking catalyst E containing USY (E) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst E are shown in Table 3.

Example 6 Hydrocracking Catalyst F

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by sulfuric acid of 25%by mass. Hafnium chloride 8 g and titanyl sulfate of 33% by mass 60 gwere added and mixed, and the suspension was stirred at room temperaturefor 3 hours. Then, the pH was adjusted to 7.2 by aqueous ammonia of 15%by mass, and the suspension was stirred at room temperature for 1 hourand then filtrated. A matter obtained was washed with 10 L of water anddried at 130° C. for 20 hours to obtain about 1 kg of ahafnium⋅titanium-substituted type zeolite (hereinafter referred to as“USY (F)”). The properties of USY (F) are shown in Table 2.

Further, a hydrocracking catalyst F containing USY (F) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst F are shown in Table 3.

Comparative Example 1 Hydrocracking Catalyst G

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by sulfuric acid of 25%by mass. Titanyl sulfate of 33% by mass 60 g was added and mixed, andthe suspension was stirred at room temperature for 3 hours. Then, the pHwas adjusted to 7.2 by aqueous ammonia of 15% by mass, and thesuspension was stirred at room temperature for 1 hour and thenfiltrated. A matter obtained was washed with 10 L of water and dried at130° C. for 20 hours to obtain about 1 kg of a titanium-substituted typezeolite (hereinafter referred to as “USY (G)”). The properties of USY(G) are shown in Table 2.

Further, a hydrocracking catalyst G containing USY (G) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst G are shown in Table 3.

Comparative Example 2 Hydrocracking Catalyst H

USY (b) 1 kg before calcining obtained in Example 1 was suspended in 10L of water of 25° C., and a pH of the solution was adjusted to 1.6 bysulfuric acid of 25% by mass. Zirconium sulfate of 18% by mass 86 g wasadded and mixed, and the suspension was stirred at room temperature for3 hours. Then, the pH was adjusted to 7.2 by aqueous ammonia of 15% bymass, and the suspension was stirred at room temperature for 1 hour andthen filtrated. A matter obtained was washed with 10 L of water anddried at 130° C. for 20 hours to obtain about 1 kg of azirconium-substituted type zeolite (hereinafter referred to as “USY(H)”). The properties of USY (H) are shown in Table 2, and a UV spectrumof USY (H) is shown in FIG. 3. In FIG. 3, it was observed fromcomparison of the UV spectra of USY (H) and USY (A) that substitutionwith zirconium was accelerated by calcining.

Further, a hydrocracking catalyst H containing USY (H) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst H are shown in Table 3.

Comparative Example 3 Hydrocracking Catalyst I

An ultra stable Y-type zeolite (hereinafter referred to as “USY (d)”) 1kg prepared by calcining USY (b) obtained in Example 1 at 400° C. forone hour was suspended in 10 L of water of 25° C., and a pH of thesolution was adjusted to 1.6 by sulfuric acid of 25% by mass. Zirconiumsulfate of 18% by mass 86 g was added and mixed, and the suspension wasstirred at room temperature for 3 hours. Then, the pH was adjusted to7.2 by aqueous ammonia of 15% by mass, and the suspension was stirred atroom temperature for 1 hour and then filtrated. A matter obtained waswashed with 10 L of water and dried at 130° C. for 20 hours to obtainabout 1 kg of a zirconium-substituted type zeolite (hereinafter referredto as “USY (I)”). In this regard, the properties of USY (d) are shown inTable 1; the properties of USY (I) are shown in Table 2; and a UVspectrum of USY (I) is shown in FIG. 3.

In FIG. 3, it was found from comparison of the UV spectra of USY (I) andUSY (A) that substitution with zirconium was not accelerated bycalcining at 400° C.

Further, a hydrocracking catalyst I containing USY (I) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst I are shown in Table 3.

Comparative Example 4 Hydrocracking Catalyst J

An ultra stable Y-type zeolite (hereinafter referred to as “USY (e)”) 1kg prepared by calcining USY (b) obtained in Example 1 at 800° C. forone hour was suspended in 10 L of water of 25° C., and a pH of thesolution was adjusted to 1.6 by sulfuric acid of 25% by mass. Zirconiumsulfate of 18% by mass 86 g was added and mixed, and the suspension wasstirred at room temperature for 3 hours. Then, the pH was adjusted to7.2 by aqueous ammonia of 15% by mass, and the suspension was stirred atroom temperature for 1 hour and then filtrated. A matter obtained waswashed with 10 L of water and dried at 130° C. for 20 hours to obtainabout 1 kg of a zirconium-substituted type zeolite (hereinafter referredto as “USY (J)”). The properties of USY (e) are shown in Table 1; theproperties of USY (J) are shown in Table 2; and a UV spectrum of USY (J)is shown in FIG. 3.

Further, a hydrocracking catalyst J containing USY (J) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst J are shown in Table 3.

Comparative Example 5 Hydrocracking Catalyst K

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 0.6 by sulfuric acid of 25%by mass. Zirconium sulfate of 18% by mass 86 g was added and mixed, andthe suspension was stirred at room temperature for 3 hours. Then, the pHwas adjusted to 7.2 by aqueous ammonia of 15% by mass, and the solutionwas stirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a zirconium-substituted type zeolite(hereinafter referred to as “USY (K)”). The properties of USY (K) areshown in Table 2.

Further, a hydrocracking catalyst K containing USY (K) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst K are shown in Table 3.

Comparative Example 6 Hydrocracking Catalyst L

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 2.4 by sulfuric acid of 25%by mass. Zirconium sulfate of 18% by mass 86 g was added and mixed, andthe suspension was stirred at room temperature for 3 hours. Then, the pHwas adjusted to 7.2 by aqueous ammonia of 15% by mass, and thesuspension was stirred at room temperature for 1 hour and thenfiltrated. A matter obtained was washed with 10 L of water and dried at130° C. for 20 hours to obtain about 1 kg of a zirconium-substitutedtype zeolite (hereinafter referred to as “USY (L)”). The properties ofUSY (L) are shown in Table 2.

Further, a hydrocracking catalyst L containing USY (L) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst L are shown in Table 3.

Comparative Example 7 Hydrocracking Catalyst M

USY (a) 2 kg obtained in Example 1 was suspended in 20 L of warm waterof 60° C. Sulfuric acid of 25 mass % 3.7 kg was gradually added to theabove suspension and then stirred at 70° C. for one hour to dissolveextraskeletal aluminum. Then, the suspension was filtrated, and a matterobtained was washed with 20 liter of purified water of 60° C. and driedat 130° C. for 20 hours to obtain an ultra stable Y-type zeolite(hereinafter referred to as “USY (f)”). The properties of USY (f) areshown in Table 1.

USY (f) thus obtained was calcined at 600° C. for 1 hour to obtain about1.5 kg of an ultra stable Y-type zeolite (hereinafter referred to as“USY (g)”). The properties of USY (g) are shown in Table 1.

USY (g) 1 kg thus obtained was suspended in 10 L of water of 25° C., anda pH of the solution was adjusted to 1.6 by sulfuric acid of 25% bymass. Zirconium sulfate of 18% by mass 86 g was added and mixed, and thesuspension was stirred at room temperature for 3 hours. Then, the pH wasadjusted to 7.2 by aqueous ammonia of 15% by mass, and the suspensionwas stirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a zirconium-substituted type zeolite(hereinafter referred to as “USY (M)”). The properties of USY (M) areshown in Table 2.

Further, a hydrocracking catalyst M containing USY (M) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst M are shown in Table 3.

Comparative Example 8 Hydrocracking Catalyst N

USY (a) 2 kg obtained in Example 1 was suspended in 20 L of warm waterof 60° C. Sulfuric acid of 25 mass % 13.6 kg was gradually added to theabove suspension and then stirred at 70° C. for one hour to dissolveextraskeletal aluminum. Then, the suspension was filtrated, and a matterobtained was washed with 20 liter of water of 60° C. and dried at 130°C. for 20 hours to obtain an ultra stable Y-type zeolite (hereinafterreferred to as “USY (h)”). The properties of USY (h) are shown in Table1.

USY (h) thus obtained was calcined at 600° C. for 1 hour to obtain about11 kg of an ultra stable Y-type zeolite (hereinafter referred to as “USY(i)”). The properties of USY (i) are shown in Table 1.

USY (i) 1 kg thus obtained was suspended in 10 L of water of 25° C., anda pH of the solution was adjusted to 1.6 by sulfuric acid of 25% bymass. Zirconium sulfate of 18% by mass 86 g was added and mixed, and thesuspension was stirred at room temperature for 3 hours. Then, the pH wasadjusted to 7.2 by aqueous ammonia of 15% by mass, and the suspensionwas stirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a zirconium-substituted type zeolite(hereinafter referred to as “USY (N)”). The properties of USY (N) areshown in Table 2.

Further, a hydrocracking catalyst N containing USY (N) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst N are shown in Table 3.

Comparative Example 9 Hydrocracking Catalyst O

NH₄ ⁹⁵Y 2 kg obtained in Example 1 was calcined at 800° C. for one hourin a saturated water vapor atmosphere to obtain about 15 kg of an ultrastable Y-type zeolite (hereinafter referred to as “USY (j)”) having a UDof 2.425 nm. The properties of USY (j) are shown in Table 1.

USY (j) 1 kg thus obtained was calcined at 600° C. for 1 hour to obtain1.5 kg of an ultra stable Y-type zeolite (hereinafter referred to as“USY (k)”). The properties of USY (k) are shown in Table 1.

USY (k) 1 kg thus obtained was suspended in 10 L of water of 25° C., anda pH of the solution was adjusted to 1.6 by a sulfuric acid aqueoussolution of 25% by mass. Zirconium sulfate of 18% by mass 86 g was addedand mixed, and the suspension was stirred at room temperature for 3hours. Then, the pH was adjusted to 7.2 by aqueous ammonia of 15% bymass, and the suspension was stirred at room temperature for 1 hour andthen filtrated. A matter obtained was washed with 10 L of water anddried at 130° C. for 20 hours to obtain about 1 kg of azirconium-substituted type zeolite (hereinafter referred to as “USY(O)”). The properties of USY (O) are shown in Table 2.

Further, a hydrocracking catalyst O containing USY (O) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst O are shown in Table 3.

Comparative Example 10 Hydrocracking Catalyst P

NH₄ ⁹⁵Y 2 kg obtained in Example 1 was calcined at 800° C. for one hourin a saturated water vapor atmosphere to obtain an ultra stable Y-typezeolite (hereinafter referred to as “USY (l)”) having a UD of 2.455 nm.The properties of USY (l) are shown in Table 1.

USY (l) thus obtained was calcined at 600° C. for 1 hour to obtain about1.5 kg of an ultra stable Y-type zeolite (hereinafter referred to as“USY (m)”). The properties of USY (m) are shown in Table 1.

USY (m) 1 kg thus obtained was suspended in 10 L of water of 25° C., anda pH of the solution was adjusted to 1.6 by a sulfuric acid aqueoussolution of 25% by mass. Zirconium sulfate of 18% by mass 86 g was addedand mixed, and the suspension was stirred at room temperature for 3hours. Then, the pH was adjusted to 7.2 by aqueous ammonia of 15% bymass, and the suspension was stirred at room temperature for 1 hour andthen filtrated. A matter obtained was washed with 10 L of water anddried at 130° C. for 20 hours to obtain about 1 kg of azirconium-substituted type zeolite (hereinafter referred to as “USY(P)”). The properties of USY (P) are shown in Table 2.

Further, a hydrocracking catalyst P containing USY (P) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst P are shown in Table 3.

Comparative Example 11 Hydrocracking Catalyst Q

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by a sulfuric acidaqueous solution of 25% by mass. Zirconium sulfate of 18% by mass 8.6 gwas added and mixed, and the suspension was stirred at room temperaturefor 3 hours. Then, the pH was adjusted to 7.2 by aqueous ammonia of 15%by mass, and the suspension was stirred at room temperature for 1 hourand then filtrated. A matter obtained was washed with 10 L of water anddried at 130° C. for 20 hours to obtain about 1 kg of azirconium-substituted type zeolite (hereinafter referred to as “USY(Q)”). The properties of USY (Q) are shown in Table 2.

Further, a hydrocracking catalyst Q containing USY (Q) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst Q are shown in Table 3.

Comparative Example 12 Hydrocracking Catalyst R

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by a sulfuric acidaqueous solution of 25% by mass. Zirconium sulfate of 18% by mass 516 gwas added and mixed, and the suspension was stirred at room temperaturefor 3 hours. Then, the pH was adjusted to 7.2 by aqueous ammonia of 15%by mass, and the suspension was stirred at room temperature for 1 hourand then filtrated. A matter obtained was washed with 10 L of water anddried at 130° C. for 20 hours to obtain about 1 kg of azirconium-substituted type zeolite (hereinafter referred to as “USY(Q)”). The properties of USY (Q) are shown in Table 2.

Further, a hydrocracking catalyst Q containing USY (Q) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst Q are shown in Table 3.

Comparative Example 13 Hydrocracking Catalyst S

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by a sulfuric acidaqueous solution of 25% by mass. Hafnium chloride 1.6 g was added andmixed, and the suspension was stirred at room temperature for 3 hours.Then, the pH was adjusted to 7.2 by aqueous ammonia of 15% by mass, andthe suspension was stirred at room temperature for 1 hour and thenfiltrated. A matter obtained was washed with 10 L of water and dried at130° C. for 20 hours to obtain about 1 kg of a hafnium-substituted typezeolite (hereinafter referred to as “USY (S)”). The properties of USY(S) are shown in Table 2.

Further, a hydrocracking catalyst S containing USY (S) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst S are shown in Table 3.

Comparative Example 14 Hydrocracking Catalyst T

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by a sulfuric acidaqueous solution of 25% by mass. Hafnium chloride 96 g was added andmixed, and the suspension was stirred at room temperature for 3 hours.Then, the pH was adjusted to 7.2 by aqueous ammonia of 15% by mass, andthe suspension was stirred at room temperature for 1 hour and thenfiltrated. A matter obtained was washed with 10 L of water and dried at130° C. for 20 hours to obtain about 1 kg of a hafnium-substituted typezeolite (hereinafter referred to as “USY (T)”). The properties of USY(T) are shown in Table 2.

Further, a hydrocracking catalyst T containing USY (T) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst T are shown in Table 3.

Comparative Example 15 Hydrocracking Catalyst U

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by a sulfuric acidaqueous solution of 25% by mass. Zirconium sulfate of 18% by mass 86 gand titanyl sulfate of 33% by mass 6.0 g were added and mixed, and thesuspension was stirred at room temperature for 3 hours. Then, the pH wasadjusted to 7.2 by aqueous ammonia of 15% by mass, and the suspensionwas stirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a zirconium⋅titanium-substituted type zeolite(hereinafter referred to as “USY (U)”). The properties of USY (U) areshown in Table 2.

Further, a hydrocracking catalyst U containing USY (U) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst U are shown in Table 3.

Comparative Example 16 Hydrocracking Catalyst V

USY (c) 1 kg obtained in Example 1 was suspended in 10 L of water of 25°C., and a pH of the solution was adjusted to 1.6 by a sulfuric acidaqueous solution of 25% by mass. Zirconium sulfate of 18% by mass 86 gand titanyl sulfate of 33% by mass 516 g were added and mixed, and thesuspension was stirred at room temperature for 3 hours. Then, the pH wasadjusted to 7.2 by aqueous ammonia of 15% by mass, and the suspensionwas stirred at room temperature for 1 hour and then filtrated. A matterobtained was washed with 10 L of water and dried at 130° C. for 20 hoursto obtain about 1 kg of a zirconium⋅titanium-substituted type zeolite(hereinafter referred to as “USY (V)”). The properties of USY (V) areshown in Table 2.

Further, a hydrocracking catalyst V containing USY (V) was prepared inthe same manner as in Example 1. The properties of the hydrocrackingcatalyst V . . . are shown in Table 3.

TABLE 1 Crystal Specific Silica- lattice surface alumina constant areaCrystallinity USY ratio (nm) (m²/g) (%) a 5.2 2.438 635 98 b 30.2 2.436710 105 c 30.1 2.436 712 105 d 30.2 2.438 710 105 e 30.1 2.435 708 103 f15.5 2.437 705 104 g 15.6 2.437 702 103 h 126 2.434 703 101 i 125 2.434705 101 j 30.8 2.428 585 88 k 30.5 2.428 583 87 l 29.5 2.455 685 98 m29.3 2.454 688 97

TABLE 2 Crystal Specific Silica- Lattice surface alumina constant areaCrystallinity ZrO₂ HfO₂ TiO₂ USY ratio (nm) (m²/g) (%) (mass %) (mass %)(mass %) Example 1 A 29.8 2.438 710 105 1.01 — — Example 2 B 30.7 2.438735 108 — 0.49 — Example 3 C 30.5 2.437 716 103 0.99 0.50 — Example 4 D29.5 2.435 701 88 0.98 0.49 1.03 Example 5 E 29.6 2.436 697 83 0.96 —0.98 Example 6 F 30.0 2.435 696 89 — 0.50 1.01 Comparative G 29.6 2.437698 92 — — 1.02 Example 1 Comparative H 29.6 2.437 712 105 0.99 — —Example 2 Comparative I 29.7 2.439 718 102 0.99 — — Example 3Comparative J 30.0 2.433 701 103 0.99 — — Example 4 Comparative K 30.12.436 702 105 0.98 — — Example 5 Comparative L 30.1 2.436 708 104 1.00 —— Example 6 Comparative M 15.6 2.438 722 105 0.97 — — Example 7Comparative N 124.0 2.432 748 102 1.01 — — Example 8 Comparative O 30.82.428 710 101 0.98 — — Example 9 Comparative P 29.5 2.456 706 105 0.99 —— Example 10 Comparative Q 29.9 2.437 714 106 0.10 — — Example 11Comparative R 30.0 2.437 708 103 6.03 — — Example 12 Comparative S 30.52.436 733 107 — 0.13 — Example 13 Comparative T 30.3 2.437 704 99 — 6.02— Example 14 Comparative U 29.8 2.437 700 105 0.98 — 0.12 Example 15Comparative V 30.0 2.436 696 93 0.99 — 6.04 Example 16

TABLE 3 Specific surface Pore ZrO₂ HfO₂ TiO₂ MoO₃ NiO area volumeCatalyst (mass %) (mass %) (mass %) (mass %) (mass %) (m²/g) (ml/g)Example 1 A 0.39 — — 16.7 3.88 384 0.56 Example 2 B — 0.19 — 16.1 3.92364 0.55 Example 3 C 0.40 0.20 — 16.0 3.90 372 0.54 Example 4 D 0.410.21 0.39 16.3 3.78 380 0.56 Example 5 E 0.39 — 0.40 16.2 3.82 375 0.52Example 6 F — 0.20 0.40 16.4 3.72 366 0.58 Comparative G — — 0.41 15.73.84 364 0.51 Example 1 Comparative H 0.38 — — 16.4 3.75 368 0.54Example 2 Comparative I 0.39 — — 15.9 3.73 379 0.51 Example 3Comparative J 0.38 — — 16.4 3.75 368 0.54 Example 4 Comparative K 0.39 —— 16.2 3.80 376 0.51 Example 5 Comparative L 0.38 — — 16.1 3.85 375 0.50Example 6 Comparative M 0.40 — — 16.0 3.90 380 0.51 Example 7Comparative N 0.41 — — 15.7 3.83 357 0.53 Example 8 Comparative O 0.42 —— 16.5 3.82 382 0.57 Example 9 Comparative P 0.40 — — 15.9 3.83 383 0.53Example 10 Comparative Q 0.01 — — 16.2 3.87 380 0.50 Example 11Comparative R 2.39 — — 16.1 3.92 372 0.52 Example 12 Comparative S —0.01 — 16.0 3.80 384 0.51 Example 13 Comparative T — 2.40 — 16.4 3.99380 0.53 Example 14 Comparative U 0.39 — 0.01 15.9 3.81 382 0.50 Example15 Comparative V 0.40 — 2.41 16.3 3.88 380 0.52 Example 16

Test Example Catalyst Activity Evaluation

Hydrocracking reactor was carried out on the conditions of a hydrogenpartial pressure of 13 MPa, a liquid hourly space velocity of 0.26 hr⁻¹,a hydrogen-to-oil ratio (hydrogen/oil ratio) of 1250 Nm³/kL and areactor temperature of 370° C. using the catalysts A to X andhydrocarbon oils having properties shown in Table 4 as raw material oilsby means of a fixed bed flow type reactor equipment manufactured byXytel Corporation to determine decomposition rates according to thefollowing equation (2) and middle distillate (kerosene and light oil)yields according to the following equation (3). The catalyst activitieswere evaluated according to the following procedures 1) and 2) based onthe values of the decomposition rates and the middle distillate yields.

1) A ratio of a value of a decomposition rate of the other catalyst to avalue of a decomposition rate of the catalyst A was determined and shownin terms of a relative decomposition rate, wherein a decomposition rateof the catalyst A was set to 100. The results thereof are shown in Table5.

2) A ratio of a yield of the middle distillate of the other catalyst toa yield of the middle distillate of the catalyst A was determined andshown in terms of a relative yield of the middle distillate, wherein ayield of the middle distillate of the catalyst A was set to 100. Theresults thereof are shown in Table 5.

Decomposition rate (%)=(content (kg) of a fraction having

-   -   a boiling point of higher than 375° C. in the produced        oil)/(content (kg) of a fraction having a boiling point of        higher than 375° C. in the raw oil)×100

-   Yield (%) of the middle distillate=(content (kg) of a fraction    having a boiling point of 149 to 375° C. in the produced    oil)/(content (kg) of a fraction having a boiling point of lower    than 375° C. in the raw oil)×100    In this connection, “%” means “% by mass” in both of the    decomposition rate and the middle distillate yield.

According to the results shown in Table 5, at least one side of thedecomposition rates and the middle distillate yields in the catalysts(catalysts A to F) according to the present invention shows high valuesas compared with those of the catalysts (catalysts G to V) of thecomparative examples, and the others than the above ones show at leastthe equivalent values. This means that a superiority of the catalystsaccording to the present invention is shown.

TABLE 4 Specific gravity (g/ml) 0.9203 Sulfur content (mass %) 2.23Nitrogen content (weight ppm) 815 C5 to 85° C. (mass %) 0 85 to 149° C.(mass %) 0 149 to 185° C. (mass %) 0 185 to 240° C. (mass %) 1.3 240 to315° C. (mass %) 2.7 315 to 375° C. (mass %) 8.0 375 to 560° C. (mass %)79.5 560° C.⁺ (mass %) 8.5

TABLE 5 Relative Relative middle decomposition distillate Catalyst rate(%) yield (%) Example 1 A 100 100 Example 2 B 99 97 Example 3 C 99 96Example 4 D 100 95 Example 5 E 99 96 Example 6 F 100 96 Comparative G 9991 Example 1 Comparative H 98 93 Example 2 Comparative I 97 92 Example 3Comparative J 96 89 Example 4 Comparative K 98 91 Example 5 ComparativeL 98 91 Example 6 Comparative M 97 91 Example 7 Comparative N 99 89Example 8 Comparative O 99 90 Example 9 Comparative P 97 92 Example 10Comparative Q 99 94 Example 11 Comparative R 98 93 Example 12Comparative S 98 94 Example 13 Comparative T 97 92 Example 14Comparative U 98 94 Example 15 Comparative V 95 90 Example 16

Example 7 Hydrocracking Catalyst W

Silica gel having 7 mass % of silica was obtained by addition of waterglass having 8.5 mass % of silica to 25 mass % of sulfuric acid aqueoussolution. On the other hand, alumina slurry was obtained by mixing 40 kgof sodium aluminium dioxide aqueous solution having 6.8 mass % of Al2O3and 40 kg of aluminium sulfate aqueous solution having 2.4 mass % ofAl2O3. Above described silica gel and alumina slurry were mixed in themass ratio of 70:30, and stirred at 60° C. for 1 hour. After filtration,product was washed by 150 ml of aqueous ammonium solution of 0.3 mass %of ammonia in order to remove Na2SO4. Further, the product was dilutedby water to produce 10 mass % of water slurry and its pH was controlledat 10.5 by addition of 15 mass % of aqueous ammonium solution. Then, itwas stirred at 95° C. for 10 hours, being removed of water, washed andkneaded to provide silica-alumina product.

The silica-alumina obtained was mixed with USY (A) in the ratio ofsilica-alumina:USY=1.5:1 in dry mass base, then being kneaded,extrudated to cylinder shape of 1.8 mm diameter, dried and calcined at550° C. for 3 hours to provide support W.

Further, hydrocracking catalyst W was prepared by the same manner asexample 1. Compositions and physical properties of hydrocrackingcatalyst W are shown in the Table 6.

TABLE 6 Inorganic Specific oxide Inorganic surface Pore Alumina:Silicaoxide:USY ZrO₂ MoO₃ NiO area volume Catalyst (mass ratio) USY (massratio) (mass %) (mass %) (mass %) (m²/g) (ml/g) Example 7 W 70:30 A1.5:1   0.31 16.2 3.72 387 0.62 Example 8 X 70:30 A 2:1 0.27 16.3 3.78365 0.58 Example 9 Y 30:70 A 2:1 0.26 16.5 3.87 380 0.61

Example 8 Hydrocracking Catalyst X

Silica gel having 7 mass % of silica was obtained by addition of waterglass having 8.5 mass % of silica to 25 mass % of sulfuric acid aqueoussolution. On the other hand, alumina slurry was obtained by mixing 40 kgof sodium aluminium dioxide aqueous solution having 6.8 mass % of Al2O3and 40 kg of aluminium sulfate aqueous solution having 2.4 mass % ofAl2O3. Above described silica gel and alumina slurry were mixed in themass ratio of 70:30, and stirred at 60° C. for 1 hour. After filtration,product was washed by 150 ml of aqueous ammonium solution of 0.3 mass %of ammonia in order to remove Na2SO4. Further, the product was dilutedby water to produce 10 mass % of water slurry and its pH was controlledat 10.5 by addition of 15 mass % of aqueous ammonium solution. Then, itwas stirred at 95° C. for 10 hours, being removed of water, washed andkneaded to provide silica-alumina product.

The silica-alumina obtained was mixed with USY (A) in the ratio ofsilica-alumina:USY=2:1 in dry mass base, then being kneaded, extrudatedto cylinder shape of 1.8 mm diameter, dried and calcined at 550° C. for3 hours to provide support X.

Further, hydrocracking catalyst X was prepared by the same method asexample 1. Compositions and physical properties of hydrocrackingcatalyst X are shown in the Table 6.

Example 9 Hydrocracking Catalyst Y

Silica gel having 7 mass % of silica was obtained by addition of waterglass having 8.5 mass % of silica to 25 mass % of sulfuric acid aqueoussolution. On the other hand, alumina slurry was obtained by mixing 40 kgof sodium aluminium dioxide aqueous solution having 6.8 mass % of Al2O3and 40 kg of aluminium sulfate aqueous solution having 2.4 mass % ofAl2O3. Above described silica gel and alumina slurry were mixed in themass ratio of 30:70, and stirred at 60° C. for 1 hour. After filtration,product was washed by 150 ml of aqueous ammonium solution of 0.3 mass %of ammonia in order to remove Na2SO4. Further, the product was dilutedby water to produce 10 mass % of water slurry and its pH was controlledat 10.5 by addition of 15 mass % of aqueous ammonium solution. Then, itwas stirred at 95° C. for 10 hours, being removed of water, washed andkneaded to provide silica-alumina product.

The silica-alumina obtained was mixed with USY(A) in the ratio ofsilica-alumina:USY=2:1 in dry mass base, then being kneaded, extrudatedto cylinder shape of 1.8 mm diameter, dried and calcined at 550° C. for3 hours to provide support Y.

Further, hydrocracking catalyst Y was prepared by the same method asexample 1. Compositions and physical properties of hydrocrackingcatalyst Y are shown in the Table 6.

Activity of the prepared catalyst W, X and Y were evaluated by using thesame method as above described. The results are shown in Table 7.

TABLE 7 Relative Relative middle decomposition distillate rate yieldCatalyst (%) (%) Example 7 W 102 98 Example 8 X 98 106 Example 9 Y 102105

As can be seen in Table 7, high cracking activity and middle distillateselectivity are obtained for the catalysts having alumina-silica assupport as well as alumina support.

Generally speaking, in comparison with alumina, since alumina-silica hasrelatively strong acidic site, it has higher cracking activity in spiteof lower USY zeolite content. As a result, alumina-silica has highermiddle distillate selectivity than alumina with USY zeolite.

The present invention shall not be restricted to the embodimentsdescribed above and can be changed as long as the scope of the presentinvention is not changed. For example, cases in which a part or all ofthe respective embodiments and modification examples each describedabove are combined to constitute the hydrocracking catalysts forhydrocarbon oil according to the present invention and the hydrotreatingmethod in which the above catalysts are used are included as well in thescope of right in the present invention.

For example, in the hydrocracking catalysts for hydrocarbon oil in theembodiments described above, the hydrocracking catalyst for hydrocarbonoil according to the present invention may be mixed in advance with thecatalyst (Y) to fill the catalyst filling baths of the respective stageswith the mixed catalyst.

What is claimed is:
 1. A hydrocracking catalyst for hydrocarbon oilcomprising a hydrogenative metal component carried on a supportcontaining an ultra-stable Y-type zeolite, wherein the aboveultra-stable Y-type zeolite is a framework-substituted zeolite(hereinafter referred to as a framework-substituted zeolite-1) in whicha part of aluminum atoms constituting a zeolite framework thereof issubstituted with 0.1-5 mass % zirconium atoms and 0.1-5 mass % titaniumions calculated on an oxide basis.
 2. A hydrocracking catalyst forhydrocarbon oil according to claim 1, wherein said zeolite-1 containsfrom 0.1 to 5 mass % hafnium atoms as calculated as the oxide basis. 3.The hydrocracking catalyst for hydrocarbon oil according to claim 1,wherein the support contains the framework-substituted zeolite-1 andinorganic oxide excluding the framework-substituted zeolite-1.
 4. Thehydrocracking catalyst for hydrocarbon oil according to claim 3, whereinthe inorganic oxide is alumina and/or silica-alumina.
 5. Thehydrocracking catalyst for hydrocarbon oil according to claim 1, whereinthe support further contains a titanium-substituted zeolite of which atleast a part of aluminum atoms constituting a framework of theultra-stable Y-type zeolite is substituted only with titanium atoms. 6.The hydrocracking catalyst for hydrocarbon oil according to claim 5,wherein said titanium-substituted zeolite contains from 0.1 to 5 mass %titanium atoms as calculated as the oxide basis.
 7. The hydrocrackingcatalyst for hydrocarbon oil according to claim 5, wherein the supportcomprises the framework-substituted zeolite-1, the titanium-substitutedzeolite and inorganic oxide excluding the framework-substitutedzeolite-1 and the framework-substituted zeolite-2.
 8. The hydrocrackingcatalyst for hydrocarbon oil according to claim 1, wherein theframework-zeolite-1 has the following characteristics: (a) a crystallattice constant of 2.430 to 2.450 nm, (b) a specific surface area of600 to 900 m²/g, and (c) a molar ratio of SiO₂ to Al₂O₃ of 20 to
 100. 9.The hydrocracking catalyst for hydrocarbon oil according to claim 1,having a specific surface area of 200 to 450 m²/g; a volume of poreshaving a diameter of 600 A or less of 0.40 to 0.75 ml/g; and a carryingamount of a hydrogenative metal component falls of 0.01 to 40 mass %.10. A method for hydrocracking hydrocarbon oil, comprising:hydrocracking hydrocarbon oil with the hydrocracking catalyst accordingto claim
 1. 11. The method for hydrocracking hydrocarbon oil accordingto claim 10, further comprising: filling a hydrotreating apparatus whichis a flow reactor with the hydrocracking catalyst; and treating ahydrocarbon oil having a boiling point of 375° C. to 833° C. in thepresence of hydrogen at a reactor temperature of 300° C. to 500° C., ahydrogen pressure of 4 to 30 MPa, a liquid hourly space velocity (LHSV)of 0.1 to 10 h⁻¹, and a hydrogen/oil ratio of 500 to 2500 Nm³/m³. 12.The method for hydrocracking hydrocarbon oil according to claim 11,wherein the flow reactor is a flow reactor selected from the groupconsisting of a stirred tank, a ebullient bed reactor, a baffled slurrytank, a fixed bed reactor, a rotating tubular reactor and a slurry-bedreactor.
 13. The method for hydrocracking hydrocarbon oil according toclaim 11, wherein the hydrocarbon oil comprises refined oil obtainedfrom (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sand,(5) shale oil or (6) coal oil.
 14. The method for hydrocrackinghydrocarbon oil according to claim 11, wherein the hydrocarbon oilcomprises refined oil obtained from crude oil, synthetic crude oil,bitumen, oil sand, shale oil or coal oil, and said refined oil is a)vacuum gas oil (VGO), b) deasphalted oil (DAO) obtained from a solventdeasphalting process or demetalized oil, c) light coker gas oil or heavycoker gas oil obtained from a coker process, d) cycle oil obtained froma fluid catalytic cracking (FCC) process or e) gas oil obtained from avisbraking process.
 15. The method for hydrocracking hydrocarbon oilaccording to claim 10, further comprising: filling a hydrotreatingapparatus which is a flow reactor with the hydrocracking catalyst; andtreating a hydrocarbon oil having a boiling point of 375° C. to 650° C.in the presence of hydrogen at a reactor temperature of 330° C. to 450°C., a hydrogen pressure of 7 to 15 MPa, a liquid hourly space velocity(LHSV) of 0.2 to 1.5h⁻¹, and a hydrogen/oil ratio of 1000 to 2000 Nm³/m³to afford kerosene-gas oil.